US5023285A - Bis (tri-tertiary-alkylphenoxy) diphosphaspiroundecanes - Google Patents

Bis (tri-tertiary-alkylphenoxy) diphosphaspiroundecanes Download PDF

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US5023285A
US5023285A US07/223,318 US22331888A US5023285A US 5023285 A US5023285 A US 5023285A US 22331888 A US22331888 A US 22331888A US 5023285 A US5023285 A US 5023285A
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butyl
tert
bis
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polymer
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William E. Horn
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Borg Warner Corp
GE Specialty Chemicals Inc
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GE Specialty Chemicals Inc
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Assigned to BORG-WARNER SPECIALTY CHEMICALS, INC., A CORP. OF DE reassignment BORG-WARNER SPECIALTY CHEMICALS, INC., A CORP. OF DE ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: HORN, WILLIAM E.
Priority to AU37882/89A priority patent/AU623155B2/en
Priority to EP89113222A priority patent/EP0356687B1/de
Priority to ES89113222T priority patent/ES2054944T3/es
Priority to DE68916340T priority patent/DE68916340T2/de
Priority to JP1191212A priority patent/JPH0280439A/ja
Priority to CS894467A priority patent/CZ283792B6/cs
Priority to SK4467-89A priority patent/SK446789A3/sk
Priority to KR1019890010435A priority patent/KR0163028B1/ko
Priority to PL28076189A priority patent/PL162422B1/pl
Priority to CN89106082A priority patent/CN1023706C/zh
Priority to TW078106409A priority patent/TW198050B/zh
Assigned to BORG-WARNER CORPORATION reassignment BORG-WARNER CORPORATION MERGER (SEE DOCUMENT FOR DETAILS). Assignors: BORG-WARNER CHEMICALS, INC., A CORP. OF DE (MERGING)
Assigned to GE SPECIALTY CHEMICALS, INC. reassignment GE SPECIALTY CHEMICALS, INC. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE ON 03/09/1989 Assignors: BORG-WARNER SPECIALTY CHEMICALS, INC.
Assigned to BORG-WARNER SPECIALTY CHEMICALS, INC. reassignment BORG-WARNER SPECIALTY CHEMICALS, INC. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE ON 01/25/1988 Assignors: BW - SPECIALTY CHEMICALS CORPORATION
Assigned to GE SPECIALTY CHEMICALS, INC. (FORMERLY KNOWN AS BORG-WARNER SPECIALTY CHEMICALS, INC. AND BEFORE THAT KNOWN AS BW-SPECIALTY CHEMICALS CORPORATION), A DE CORP. reassignment GE SPECIALTY CHEMICALS, INC. (FORMERLY KNOWN AS BORG-WARNER SPECIALTY CHEMICALS, INC. AND BEFORE THAT KNOWN AS BW-SPECIALTY CHEMICALS CORPORATION), A DE CORP. MERGER: BORG-WARNER CHEMICALS, INC. INTO BORG-WARNER CORPORATION; AND AN ASSIGNMENT OF BORG-WARNER CORPORATION TO BW-SPECIALITY CHEMICALS CORPORATION; AND A CHANGE OF NAME FROM BW-SPECIALITY CHEMICALS CORPORATION TO BORG-WARNER CHEMICALS,INC.; AND CHANGE OF NAME FROM BORG-WARNER CHEMICALS, INC. TO GE SOECIALITY CHEMICALS, INC.; SEE RECORD FOR DETAILS. Assignors: BORG-WARNER CORPORATION (SURVIVING CORPORATION OF A MERGER WITH BORG-WARNER CHEMICALS, INC.)
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/527—Cyclic esters

Definitions

  • the present invention relates to bis (tri-tert-alkylphenoxy) diphosphaspiroundecanes, and to bis (2,4,6-tri-t-alkylphenoxy) diphosphaspiroundecanes in particular, as well as to polymer compositions which include tri-t-alkylphenoxy diphosphaspiroundecanes in stabilizing amounts.
  • alkylphenoxy diphosphaspiroundecanes are known in the art.
  • Japanese Early Disclosure 1986-225, 191 of Oct. 9, 1986 by Tajima et al. discloses a number of bis (alkylphenoxy) diphosphaspiroundecanes, such as, bis(2-tert-butyl-4,6-dimethylphenoxy) diphosphaspiroundecane and bis(2,4-di-t-octylphenoxy) diphosphaspiroundecane.
  • Bis (alkylphenoxy) diphosphaspiroundecanes are also disclosed by Japanese Patent No. 49-128044; U.S. Pat. Nos.
  • diphosphaspiroundecane compounds known in the art include bis (2,6-di-t-butyl-4-methylphenoxy) diphosphaspiroundecane and bis (2,6-di-t-butyl-4-ethylphenoxy) diphosphaspiroundecane.
  • Virtually all commercial polymers contain one or more stabilizing compounds to protect the polymer against degradation of polymer properties by chain scission or undesired crosslinking during processing and product use. This degradation is particularly problematical with thermoplastic polymers, which typically are subjected to extreme processing temperatures. Not only does such degradation effect the physical properties of the composition, but may also cause the polymer to become discolored, thereby making the polymer aesthetically unappealing and causing the product to be rejected.
  • polymer stabilizers may be exposed to various adverse conditions during the course of their production, shipment, storage and use.
  • One such condition which may adversely affect stabilizers is excessive to moisture either in the form of humidity or wetness.
  • moisture may be excessive to moisture either in the form of humidity or wetness.
  • many stabilizers are used in the form of powders or granules, absorption of moisture may cause a stabilizer to clump or "block" thereby making the stabilizer difficult to handle during feeding and mixing operations.
  • a consequence of such moisture exposure may be hydrolysis, which frequently reduces stabilizing properties and leaves the resin vulnerable to degradation.
  • phosphites including some of the above-mentioned diphosphaspiroundecanes, may provide excellent stabilization when properly stored, either neat or after being compounded into the polymer.
  • a few phosphites such as tris(2,4-di-t-butylphenol)phosphite (TBPP), may exhibit good storage stability in humid environments, but do not provide the stabilizing efficacy of many members of the diphosphaspiroundecane class of stabilizer.
  • TBPP tris(2,4-di-t-butylphenol)phosphite
  • diphosphaspiroundecanes are capable of acting as polymer stabilizers, an improvement in the overall balance of properties would be realized if moisture resistance could be improved while maintaining excellent stabilizing properties.
  • a stabilizer which imparts good physical and color stability to a polymer while exhibiting improved resistance to moisture and hydrolysis offers significant practical advantages over many stabilizers known in the art.
  • the present invention is a composition which comprises a diphosphaspiroundecane of the general formula: ##STR1## wherein each of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is a tertiary alkyl moiety.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are selected from the group consisting of C 4 to about C 12 tertiary alkyl moieties.
  • Tertiary-butyl is the moiety which is most preferred.
  • the present invention also is directed to a stabilized polymer composition which comprises a polymer and an effective amount of the diphosphaspiroundecane of the invention.
  • Thermoplastic polymers are preferred, with polyethylene, polypropylene, polyethylene terephthalate, polyphenylene ether, polystyrene, impact polystyrene and ABS-type graft copolymers being most preferred.
  • the present invention comprises a 3,9-bis(2,4,6-tri-t-alkylphenoxy)-2,4,8,10-tetroxa-3,9-diphosphaspiro[5.5]undecane.
  • These compounds also known as bis (2,4,6-tri-t-alkylphenyl) pentaerythritol diphosphites, may be represented by the general formula: ##STR2## wherein each of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are tertiary (or "tert” or "t") alkyl moieties.
  • moieties examples include t-butyl, t-pentyl, 1,1,4,4-tertramethyl butyl, t-octyl, 1-methyl cyclohexyl, t-dodecyl and 2-phenyl-2-propyl.
  • C 4 to about C 12 moieties such as t-butyl, t-pentyl, t-octyl and t-dodecyl are preferred.
  • Relatively smaller groups such as t-butyl, t-pentyl, 1-methylcyclohexyl and 1,1,4,4-tetramethyl butyl are more preferred.
  • Tertiary butyl moieties are most preferred.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may be selected to be different, such as in 2,4-di-t-butyl-4-t-pentyl, it is preferred that R 1 , R 2 , R 3 , R 4 , R 5 and R 6 be the same.
  • diphosphaspiroundecanes of the present invention may be made by means known in the art, such as by the reaction of a tri-t-alkylphenol with 3,9-dichloro-2,4,8,10-tetroxa-3,9-diphosphaspiro[5.5]undecane (which may be formed by the reaction of pentaerythritol with phosphorous trichloride by means known in the art).
  • 3,9-bis(2,4,6-tri-t-butylphenoxy)-2,4,8,10-tetroxa-3,9-diphosphaspiro[5.5]undecane may be formed by the reaction of 2,4,6-tri-t-butylphenol with 3,9-dichloro-2,4,8,10-tetroxa-3,9-diphosphaspiro[5.5]undecane (dichloropentite).
  • 3,9-bis(2,4,6-tri-t-pentyl phenoxy)-2,4,8,10-tetroxa-3,9-diphosphaspiro [5.5] undecane may be formed by the reaction of 2,4,6-tri-t-pentyl phenol with dichloropentite.
  • bis(tri-t-alkylphenoxy)-tetroxa-diphosphaspiroundecanes may be formed by reacting the tri-t-alkylphenol corresponding to the desired tri-t-alkylphenoxy group with dichloropentite.
  • the diphosphaspiroundecanes of the present invnetion may also be made by reacting a phenol corresponding to the desired tri-t-alkylphenoxy group with phosphorous trichloride to form a tri-t-alkylphenoxy phosphorodichloridite, followed by reaction of the phosphorodichloridite with pentaerythritol to form a bis (tri-t-alkylphenoxy)-tetroxa-diphosphaspiroundecane.
  • 2,4,6-tri-t-butylphenol may be reacted with phosphorous trichloride and then with pentaerythritol to form bis(2,4,6-tri-t-butyl-phenoxy)-tetroxa-diphosphaspiroundecane.
  • 2,4,6-tri-t-dodecylphenol might be reacted with phosphorous trichloride and then with pentaerythritol to form bis(2,4,6-tri-t-docecylphenoxy)-tetroxa-diphosphaspiroundecane.
  • diphosphaspiroundecanes Procedures for forming diphosphaspiroundecanes by the dichloropentite and the phosphorodichoridite routes are known in the art.
  • the prior art may show the diphosphaspiroundecane being formed in solution in the presence of an amine, such as triethylamine, which serves as an acid acceptor by forming an insoluble hydrochloride salt
  • the diphosphaspiroundecane be formed in a tri-n-alkylamine, such as tri-n-butylamine, wherein each n-alkyl group is a C 3 or larger n-alkyl moiety, wherein the hydrochloride salt remains in solution and the diphosphaspiroundecane product is substantially insoluble.
  • the present invention also is a stabilized polymer composition which includes an effective amount of one or more of the bis (tri-t-alkylphenoxy)-tetroxa-diphosphaspiroundecanes described above.
  • An amount of the diphosphaspiroundecanes of the invention is considered to be an "effective amount", when the polymer composition containing the diphosphaspiroundecane of the invention shows improved stability in any of its physical or color properties in comparison to an analogous polymer composition which does not include a diphosphaspiroundecane of the invention.
  • the diphosphaspiroundecane of the invention be present in an amount equal to about 0.01 to about 2 parts by weight per 100 parts by weight resin (phr). Amounts of about 0.01 to about 1 phr are more preferred, although most compositions will contain about 0.025 phr or more.
  • the polymer may be any of the polymers known in the art, such as polyesters, polyurethanes, polyalkylene terephthalates, polysulfones, polyimides, polyphenylene ethers, styrenic polymers, poly carbonates, acrylic polymers, polyamides, polyacetals, halide containing polymers and polyolefin homopolymers and copolymers.
  • Mixtures of different polymers such as polyphenylene ether/styrenic resin blends, polyvinylchloride/ABS or other impact modified polymers, such as methacrylonitrile containing ABS, and polyester/ABS or polyester plus some other impact modifier may also be used.
  • diphosphaspiroundecanes of the invention are particularly useful in thermoplastic polymers, such as polyolefins, polycarbonates, polyesters, polyphenylene ethers and styrenic polymers, due to the extreme temperatures at which thermoplastic polymers are often processed and/or used.
  • Polymers of monoolefins and diolefins for example polypropylene, polyisobutylene, polybutene-1, polymethylpentene-1, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), low density polyethylene (LDPE) and linear low density polyethylene (LLDPE) may be used.
  • HDPE high density polyethylene
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • Mixtures of these polymers for example mixtures of polypropylene with (PP) polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE), may also be used.
  • copolymers of monoolefins and diolefines with each other or with other vinyl monomers such as, for example, ethylene/propylene, LLDPE and its mixtures with LDPE, propylene/butene-1, ethylene/hexene, ethylene/ethylpentene, ethylene/heptene, ethylene/octene, propylene/isobutylene, ethylene/butane-1, propylene/butadiene, isobutylene/isoprene, ethylene/alkyl acrylates, ethylene/alkyl methacrylates, ethylene/vinyl acetate (EVA) or ethylene/acrylic acid copolymers (EAA) and their salts (ionomers) and terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidene-norbornene; as well as mixtures of such
  • Thermoplastic polymers may also include styrenic polymers, such as polystyrene, poly-(p-methylstyrene), poly-(alpha-methylstyrene), copolymers of styrene or alpha-methylstyrene with dienes or acrylic derivatives, such as, for example, styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/maleic anhydride, styrene/butadiene/ethyl acrylate/styrene/acrylonitrile/methylacrylate; mixtures of high impact strength from styrene copolymers and another polymer, such as, for example, from a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block copolymers of styrene, such as, for example,
  • Styrenic polymers may additionally or alternatively include graft copolymers of styrene or alpha-methylstyrene such as, for example, styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene and maleic anhydride or maleimide on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene, styrene and alkyl acrylates or methacrylates on polybutadiene, styrene and acrylonitrile on ethylene/propylene/diene terpolymers, styrene and acrylon
  • Nitrile polymers are also useful in the polymer composition of the invention. These include homopolymers and copolymers of acrylonitrile and its analogs such as methacrylonitrile, such as polyacrylonitrile, acrylonitrile/butadiene polymers, acrylonitrile/alkyl acrylate polymers, acrylonitrile/alkyl methacrylate/butadiene polymers, ABS, and ABS which includes methacrylonitrile.
  • Acrylic acids such as acrylic acid, methacrylic acid, methyl methacrylic acid and ethacrylic acid and esters thereof may also be used.
  • Such polymers include polymethylmethacrylate, and ABS-type graft copolymers wherein all or part of the acrylonitrile-type monomer has been replaced by an acrylic acid ester or an acrylic acid amide.
  • Polymers including other acrylic-type monomers, such as acrolein, methacrolein, acrylamide and methacrylamide may also be used.
  • Halogen-containing polymers may also be useful. These include resins such as polychloroprene, epichlorohydrin homo-and copolymers, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, florinated polyvinylidene, brominated polyethylene, chlorinated rubber, vinyl chloride-vinylacetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride tercopolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl
  • thermoplastic polymers include homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bis-glycidyl ethers; polyacetals, such as polyoxymethylene and those polyoxymethylene which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or methacrylonitrile containing ABS; polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with polystyrene or polyamides; polycarbonates and polyester-carbonates; polysulfones, polyethersulfones and polyetherketones; and polyesters which are derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylol-cyclic
  • Polyamides and copolyamides which are derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, such as polyamide, 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12 and 4/6, polyamide 11, polyamide 12, aromatic polyamides obtained by condensation of m-xylene, diamine and adipic acid; polyamides prepared from hexamethylene diamine and isophthalic or/and terephthalic acid and optionally an elastomer as modifier, for example poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide may be useful.
  • copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, such as for instance, with polyethylene glycol, polypropylene glycol or polytetramethylene glycols, and polyamides or copolyamides modified with EPDM or ABS may be used.
  • Polyolefin, polyalkylene terephthalate, polyphenylene ether and styrenic resins, and mixtures thereof are more preferred, with polyethylene, polypropylene, polyethylene terephthalate, polyphenylene ether homopolymers and copolymers, polystyrene, high impact polystyrene, polycarbonates and ABS-type graft copolymers and mixtures thereof being particularly preferred.
  • the resulting stabilized polymer compositions of the invention may optionally also contain various conventional additives, such as the following.
  • Alkylated monophenols for example: 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-i-butylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2-(alpha-methylcyclohexyl)-4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol.
  • Alkylated hydroquinones for example, 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone, 2,6-diphenyl-4-octadecyloxyphenol.
  • Hydroxylated thiodiphenyl ethers for example, 2,2'-thio-bis-(6-tert-butyl-4-methylphenol), 2,2'-thio-bis-(4-octylphenol), 4,4'-thio-bis-(6-tert-butyl-3-methylphenol), 4,4'-thio-bis-(6-tert-butyl-2-methylphenol).
  • Alkyliden-bisphenols for example, 2,2'-methylene-bis-(6-tert-butyl-4-methylphenol), 2,2'-methylene-bis-(6-tert-butyl-4-ethylphenol), 2,2'-methylene-bis-[4-methyl-6-(alpha-methylcyclohexyl)phenol], 2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis-(6-nonyl-4-methylphenol), 2,2'-methylene-bis-[6-(alpha-methylbenzyl)-4-nonylphenol], 2,2'-methylene-bis-[6-(alpha,alpha-dimethylbenzyl)-4-nonylphenol], 2,2'-methylene-bis-(4,6-di-tert-butylphenol), 2,2'-ethylidene-bis-(4,6-di-tert-butylphenol), 2,2'-eth
  • Benzyl compounds for example, 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, bis-(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl 3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetate, bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiolterephthalate, 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate, calcium salt of monoethyl 3,5-di-ter
  • 1.6 Acylaminophenols for example, 4-hydroxy-lauric acid anilide, 4-hydroxy-stearic acid anilide, 2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydrox-yanilino)-s-triazine, octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate.
  • esters of beta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid with monohydric or polyhydric alcohols for example, methanol, diethyleneglycol, octadecanol, triethyleneglycol, 1,6-hexanediol, pentaerythritol, neopentylglycol, tris-hydroxyethyl isocyanurate, thiodiethyleneglycol, dihydroxyethyl oxalic acid diamide.
  • esters of beta-(5-tert-butyl-4-hydroxyl-3-methylphenyl)-propionic acid with monohydric or polyhydric alcohols for example, methanol, diethyleneglycol, octadecanol, triethyleneglycol, 1,6-hexanediol, pentaerythritol, neopentylglycol, tris-hydroxyethyl isocyanurate, thiodiethyleneglycol, dihydroxyethyl oxalic acid diamide.
  • Esters of beta-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono-or polyhydric alcohols e.g. with methanol, diethylene glycol, octadecanol, triethylene glycol, 1,6-hexanediol, pentaerythritol, neopentyl glycol, tris(hydroxyethyl) isocyanurate, thiodiethylene glycol, N,N'-bis(hydroxyethyl)oxalic acid diamide.
  • UV absorbers and light stabilizers 1. UV absorbers and light stabilizers.
  • 2-(2'-Hydroxyphenyl)-benzotriazoles for example, the 5'methyl-, 3',5'-di-tert-butyl-, 5'-tert-butyl-, 5'-(1,1,3,3-tetramethylbutyl)-, 5-chloro-3',5'-di-tert-butyl-, 5-chloro-3'-tert-butyl-5'-methyl-, 3'-sec-butyl-5'-tert-butyl-, 4'-octoxy, 3',5'-di-tert-amyl-, 3',5'-bis-(alpha,alpha-dimethylbenzyl)-derivatives.
  • 2-Hydroxy-benzophenones for example, the 4-hydroxy-, 4-methoxy-, 4-octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy, 4,2',4'-trihydroxy- and 2'-hydroxy-4,4'-dimethoxy derivative.
  • Acrylates for example, alpha-cyano-beta,beta-diphenylacrylic acid ethyl ester or isooctyl ester, alpha-carbomethoxy-cinnamic acid methyl ester, alpha-cyano-beta-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester, alpha-carbomethoxy-p-methoxy-cinnamic acid methyl ester, N-(beta-carbomethoxy-beta-cyano-vinyl)-2-methyl-indoline.
  • Nickel compounds for example, nickel complexes of 2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the 1:1 or 1:2 complex, optionally with additional ligands such as n-butylamine, triethanolamine or N-cyclohexyl-di-ethanolamine, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, such as of the methyl, ethyl or butyl ester, nickel complexes of ketoximes such as of 2-hydroxy-4-methyl-penyl undecyl ketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxy-pyrazol, optionally with additional ligands.
  • additional ligands such as n-butylamine, triethanolamine or N-cyclohexyl-di-ethanolamine, nickel dibutyldithio
  • Sterically hindered amines for example bis-(2,2,6,6-tetramethylpiperidyl)-sebacate, bis-(1,2,2,6,6-pentamethylpiperidyl)-sebacate, n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonic acid bis-(1,2,2,6,6-pentamethylpiperidyl)ester, condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidine and succinic acid, condensation product of N,N'-(2,2,6,6-tetramethylpiperidyl)-hexamethylendiamine and 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine, tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate, tetrakis-(2,2,6,6-tetramethyl-4-piperidy
  • Such amines include hydroxylamines derived from hindered amines, such as di(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate; 1-hydroxy-2,2,6,6-tetramethyl-4-benzoxypiperidine; 1-hydroxy-2,2,6,6-tetramethyl-4-(3,5-di-tert-butyl-4-hydroxy hydrocinnamoyloxy)-piperidine; and N-(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl)-epsilon-caprolactam.
  • hindered amines such as di(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate; 1-hydroxy-2,2,6,6-tetramethyl-4-benzoxypiperidine; 1-hydroxy-2,2,6,6-tetramethyl-4-(3,5-di-tert-butyl-4-hydroxy hydrocinnamoyloxy)-piperidine; and
  • Oxalic acid diamides for example, 4,4'-di-octyloxy-oxanilide, 2,2'-di-octyloxy-5,5'-di-tert-butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert-butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide, N,N'-bis(3-dimethylaminopropyl)-oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixtures of ortho- and para-methoxy- as well as of o- and p-ethoxy-disubstituted oxanilides.
  • Metal deactivators for example, N,N'-diphenyloxalic acid diamide, N-salicylal-N'-salicyloylhydrazine, N,N'-bis-salicyloylhydrazine, N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine, salicyloylamino-1,2,4-triazole, bis-benzyliden-oxalic acid dihydrazide.
  • Phosphites and phosphonites for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonyl-phenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, and tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite.
  • Peroxide scavengers for example esters of beta-thiodipropionic acid, for example the lauryl stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc-dibutyl-dithiocaramate, dioctadecyldisulfide, pentaerythritol-tetrakis(beta-dodecylmercapto)-propionate.
  • esters of beta-thiodipropionic acid for example the lauryl stearyl, myristyl or tridecyl esters
  • mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole zinc-dibutyl-dithiocaramate
  • dioctadecyldisulfide pentaerythritol-tetrakis(beta
  • Polyamide stabilizers for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
  • Basic co-stabilizers for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate and K palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
  • Basic co-stabilizers for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate and K
  • Nucleating agents for example, 4-tert-butyl-benzoic acid, adipic acid, diphenylacetic acid.
  • Fillers and reinforcing agents for example, calcium carbonate, silicates, glass fibres, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.
  • the present invention may also be used in conjunction with aminoxy propanoate derivatives such as methyl-3-[N,N-dibenzylaminoxy]propanoate; ethyl-3-[N,N-dibenzylaminoxy]propanoate; 1,6-hexamethylene-bis[3-(N,N-dibenzylaminoxy)propanoate]; methyl-[2-(methyl)-3(N,N-dibenzylaminoxy)propanoate]; octadecyl-3-[N,N-dibenzyl-aminoxy]propanoic acid; tetrakis[(N,N-dibenzylaminoxy)ethyl carbonyl oxymethyl]methane; octadecyl-3-[N,N-diethyl aminoxy]propanoate; 3-[N,N-dibenzylaminoxy]propanoic acid potassium salt; and 1,6-hexamethylene bis
  • additives for example, plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flame-proofing agents, anti-static agents, blowing agents and thiosynergists such as dilaurylthiodipropionate or distearylthiodipropionate.
  • Hindered phenolic antioxidants may also be present in the polymer composition. Use of diphosphaspiroundecanes of the present invention may result in enhanced polymer protection by reducing the formation of color resulting from the presence of the phenols.
  • Such phenolic antioxidants include n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayl tetrakis-(3,5-di-tert-butyl-4-hydroxyl-hydrocinnamate), di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl-)isocyanurate, thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate).
  • additives such as oxazaphospholidines, may additionally or alternatively be present.
  • the instant compounds prevent color formation when hindered amine light stabilizers are present, such hindered amines including bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-n-butyl-2-(3,5-di-tert-butyl-4-hydroxy-benzyl)malonate; bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate; dimethylsuccinate polymer with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinethanol; and polymer of 2,4-dichloro-6-octylamino-s-triazine with N'-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene diamine.
  • hindered amines including bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-n-butyl-2-(3,5-di-tert-butyl-4-hydroxy-benzyl)malonate; bis(2,2,6,6-t
  • the diphosphaspiroundecanes of the invention may be added to the polymer at any time prior to or during fabrication into articles, and may be combined with the polymer by any of a variety of means known in the art, such as by preblending or by being fed directly into fabrication equipment.
  • the present invention may further be understood by reference to the specific embodiments outlined below, which are provided herein to illustrate various aspects of the invention, either by demonstrating an aspect of the invention, such as polymer stabilization or hydrolysis resistance, or providing a basis for comparison.
  • Acid number when measured, was determined by one of the following methods. The Sodium Butoxide Method was used to determine acid number for all examples unless indicated otherwise.
  • Bromo thymol (0.1% in 1-butanol) indicator solution is added (4-6 drops) to 100 ml of 1-butanol in a 250 ml Erlenmeyer flask.
  • the butanol is neutralized to a blue-green endpoint of pH7 with 0.02N methanolic KOH (1.32 gm KOH (ACS, 85%) in anhydrous reagent grade methanol and diluted to 1 liter and standardized against standard 0.1N HCl).
  • the sample to be tested is weighed to the nearest 0.1 gm and added to the flask. When the sample is a solid the contents of the flask are warmed slightly to 176° F. (80° C.) before addition of the sample.
  • the appropriate sample weight to be used is determined from the following table:
  • the flask After addition of the sample the flask is swirled to dissolve the sample, and the contents of the flask are then immediately titrated with 0.02N KOH (described above) to a blue-green endpoint.
  • Bromothymol blue indicator (0.1%) is prepared as described above.
  • a 2 gm sample of the material to be tested is weighed out in a 250 ml Erlenmeyer flask to the nearest 0.01 gm.
  • Methylene chloride (75 ml) is added to another Erlenmeyer flask, followed by 4-6 drops of the bromothymol indicator solution, and the resulting solution is neutralized with 0.02N sodium butoxide (0.46 gm sodium metal dissolved in anhydrous butanol, diluted to 1 liter and standardized against 0.01N HCl) to a blue-green endpoint of pH-7.
  • the neutralized methylene chloride solution is then added to the flask containing the sample and swirled to dissolve the sample.
  • the resulting solution is immediately titrated with 0.02N sodium butoxide (prepared as indicated above) to a blue-green endpoint.
  • Example 1 illustrates the preparation of a diphosphaspiroundecane of the present invention, 3,9-bis(2,4,6-tri-t-butylphenoxy)-2,4,8,10-tetroxa-3,9-diphosphaspiro[5.5]undecane.
  • Example 2 demonstrates preparation of bis(2,4,6-tri-t-butylphenoxy)-tetroxadiphosphaspiroundecane by a method preferred over the method of Example 1.
  • Example 3 demonstrates preparation of bis(2,4,6-tri-t-butylphenoxy)-tetroxadiphosphaspiroundecane by another method preferred over the method of Example 1.
  • the dry blended resin mixture was extruded at a stock temperature of 525° C. through a one-inch single screw extruder equipped with a 2-stage screw fitted with a Maddox mixer.
  • the extrudate was pelletized and reextruded for a total of seven extrusions. Material was saved from the first, third, fifth and seventh extrusions.
  • the melt flow of these samples was measured using ASTM test method D-1238, Condition E.
  • the melt flow of LLDPE generally decreases with each extrusion as the polymer undergoes degradation by an overall crosslinking reaction, thereby decreasing melt flow.
  • the efficiency of a stabilizer may therefore be evaluated by measuring its melt flow over successive extrusions and determining how close the melt flow of successive extrusions are to the melt flow of the initial extrusion.
  • the color of the retained samples was measured using a Hunter colormeter and standard techniques prescribed for use with that equipment, and comparing the yellowness index (YI) change between the first and seventh samples of each extrusion.
  • the color measurements were made on one-eighth inch by one and one-half inch diameter discs that were compression molded at 330° F. from the retained sample pellets. Higher values indicate more color development.
  • diphosphaspiroundecane products of Examples 1, 4-8 were denoted as indicated below in Table I. (All are 3,9-bis(di or tri-alkylphenoxy)-2,4,8,10-tetroxa-3,9-diphosphaspiro[5.5]undecanes. However, all numbering except that of the alkyl substituents on the phenoxy moiety have been deleted below as a matter of convenience.)
  • the 3,9-bis(2,6-di-t-butyl-4-alkylphenoxy)-2,4,8,10-tetroxa-3,9-diphosphaspiro[5.5]undecanes of Table I and of the present invention were evaluated in poly(propylene) as process stabilizers by comparing their performance in an unstabilized Ziegler-Natta process resin, Profax 6501 from Hercules.
  • the resin powder was weighed together with 250 ppm of pentaerythritol tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 500 ppm of calcium stearate, and 500 ppm of the phosphite.
  • the resulting dry blend was mixed in a Turbula blender for 45 minutes.
  • the dry blend was then extruded at a stock temperature of 525° F. to form polymer pellets.
  • the pellets were reextruded under the same conditions for a total of five extrusions.
  • Pellet samples saved from the first, third and fifth extrusions were measured for melt flow retention using ASTM D-1238, Condition L. Color measurements were made on one-eighth inch color discs compression molded from pellets retained from the first and fifth extrusions. Color measurements were done on a Hunter Colormeter. The yellowness index (YI) of the samples was used to compare the relative color of the specimens. The results of the testing appear in Table III.
  • the moisture sensitivity of the spirocyclic diphosphites of Table I and of TBPP were examined by placing the compounds into an atmospheric chamber regulated at about 80% relative humidity. The samples were maintained in the chamber and monitored for weight gain and increase in acid value (AV) with respect to time. (Weight gain is an indication of the hygroscopic nature of the compound and may reflect sample hydrolysis, while an increase in acid value is indicative of some hydrolysis occuring in the sample.) The time required for the compounds to gain 1% weight during moisture exposure was assigned as the failure point. The results are indicated below in Table IV. Acid value was measured by the Na-butoxide/methylene chloride method both before the sample was placed in the atmospheric chamber (denoted "Initial AV") and after the sample had attained a 1% weight gain (denoted "Final AV").
  • compositions tested included 0.025 phr of pentaerythritol tetrakis [3-(3,5-di-t-butyl-4-hydroxy phenyl)propionate] and 0.05 phr.
  • Ca Stearate The amount of additive compound present and the results are indicated below in Table VI.

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US07/223,318 US5023285A (en) 1988-07-25 1988-07-25 Bis (tri-tertiary-alkylphenoxy) diphosphaspiroundecanes
AU37882/89A AU623155B2 (en) 1988-07-25 1989-07-05 Bis (tri-tertiary - alkylphenoxy) diphosphaspiroundecanes
EP89113222A EP0356687B1 (de) 1988-07-25 1989-07-19 Bis (tri-tertiär-alkylphenoxy) diphosphaspiroundecane
ES89113222T ES2054944T3 (es) 1988-07-25 1989-07-19 Bis-(tri-t-alquilfenoxi) difosfaespiroundecanos.
DE68916340T DE68916340T2 (de) 1988-07-25 1989-07-19 Bis (tri-tertiär-alkylphenoxy) diphosphaspiroundecane.
KR1019890010435A KR0163028B1 (ko) 1988-07-25 1989-07-24 비스(트리-3급-알킬페녹시)디포스파스피로운데칸
CS894467A CZ283792B6 (cs) 1988-07-25 1989-07-24 Stabilizátor polymerů na bázi derivátu difosfaspiroundekanu a směsi, které ho obsahují
SK4467-89A SK446789A3 (en) 1988-07-25 1989-07-24 Agent for stabilizing polymers and polymeric mixture containing the same
JP1191212A JPH0280439A (ja) 1988-07-25 1989-07-24 ビス（トリ‐ｔ‐アルキルフエノキシ）ジホスフアスピロウンデカン
PL28076189A PL162422B1 (pl) 1988-07-25 1989-07-25 Stabilizowana kompozycja pollmeryczna PL PL
CN89106082A CN1023706C (zh) 1988-07-25 1989-07-25 含双(三叔烷基苯氧基)二磷杂螺十一烷的组合物
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0559461A1 (de) * 1992-03-05 1993-09-08 General Electric Company Vergrösserung der Farbstabilität von Polyolefinzusammensetzungen
US5308901A (en) * 1988-07-25 1994-05-03 General Electric Company 3-9-diphosphaspiroundecane-stabilized polymer compositions
US5414034A (en) * 1993-03-29 1995-05-09 General Electric Company Processing stabilizer formulations
US5420184A (en) * 1992-10-14 1995-05-30 Mitsubishi Petrochemical Co., Ltd. Thermoplastic resin composition and process for preparing the same
US5500458A (en) * 1994-09-30 1996-03-19 General Electric Company Phosphite coated polymeric particles
US5559167A (en) * 1993-07-22 1996-09-24 General Electric Company Gamma irradiated thermoplastics and articles
US5786411A (en) * 1996-12-20 1998-07-28 General Electric Company Light resistant compositions of polycarbonate and graft copolymer resins
WO2000023514A1 (en) * 1998-10-21 2000-04-27 Phillips Petroleum Company Phosphite additives in polyolefins
US6770693B2 (en) 1998-07-13 2004-08-03 Dove Chemical Corporation Blends of phosphites and antioxidants
US20050113494A1 (en) * 2003-11-21 2005-05-26 Bobsein Rex L. Phosphite additives in polyolefins
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Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3201437A (en) * 1962-06-11 1965-08-17 Union Carbide Corp Neoalkyl phosphites
JPS49128044A (de) * 1973-04-09 1974-12-07
US4066611A (en) * 1976-06-23 1978-01-03 General Electric Company Stabilized polycarbonate composition
US4094855A (en) * 1976-07-30 1978-06-13 Ciba-Geigy Corporation Hindered phenyl phosphites
US4207229A (en) * 1976-07-30 1980-06-10 Ciba-Geigy Corporation Hindered phenyl phosphites
US4290976A (en) * 1975-03-24 1981-09-22 Borg-Warner Chemicals, Inc. Process for the preparation of phenol-free phosphites
US4305866A (en) * 1976-03-04 1981-12-15 Borg-Warner Chemicals, Inc. Polyolefins stabilized with cyclic diphosphites
US4312818A (en) * 1977-08-08 1982-01-26 Ciba-Geigy Corporation Process for producing triarylphosphites
EP0038876B1 (de) * 1980-04-28 1984-10-10 ADEKA ARGUS CHEMICAL CO., Ltd. 2,6-Di-tertio-butyl-phenyl-pentaerythritol-spiro-bis-phosphite, die die Beständigkeit gegen Wärme und Licht synthetischer Harze erhöhen, Stabilisatorzusammensetzungen, die phenolische Antioxidantien und solche Phosphite enthalten, und synthetische Harzzusammensetzungen, die solche Zusammensetzungen enthalten
US4520149A (en) * 1983-12-01 1985-05-28 Gaf Corporation Elastomer compositions
GB2156358A (en) * 1984-03-23 1985-10-09 Vyzk Ustav Chem Tech Composition for heat and light stabilisation of polymers
US4585818A (en) * 1983-03-31 1986-04-29 Rohm Gmbh Flame retardant polymethyl methacrylate molding compound
EP0199997A2 (de) * 1985-03-29 1986-11-05 ADEKA ARGUS CHEMICAL CO., Ltd. Verfahren zur Herstellung von Diarylpentaerythritol
JPS62167338A (ja) * 1986-01-17 1987-07-23 Chisso Corp 難燃性ポリオレフイン組成物
US4692539A (en) * 1984-12-24 1987-09-08 Ciba-Geigy Corporation Pentaerythritol diphosphite stabilizers and process

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0776291B2 (ja) * 1986-07-28 1995-08-16 旭電化工業株式会社 耐放射線性ポリオレフイン組成物
JPH0689238B2 (ja) * 1987-04-24 1994-11-09 旭電化工業株式会社 ポリエステル・ポリマ−ブレンド組成物

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3201437A (en) * 1962-06-11 1965-08-17 Union Carbide Corp Neoalkyl phosphites
JPS49128044A (de) * 1973-04-09 1974-12-07
US4290976A (en) * 1975-03-24 1981-09-22 Borg-Warner Chemicals, Inc. Process for the preparation of phenol-free phosphites
US4305866A (en) * 1976-03-04 1981-12-15 Borg-Warner Chemicals, Inc. Polyolefins stabilized with cyclic diphosphites
US4066611A (en) * 1976-06-23 1978-01-03 General Electric Company Stabilized polycarbonate composition
US4094855A (en) * 1976-07-30 1978-06-13 Ciba-Geigy Corporation Hindered phenyl phosphites
US4207229A (en) * 1976-07-30 1980-06-10 Ciba-Geigy Corporation Hindered phenyl phosphites
US4312818A (en) * 1977-08-08 1982-01-26 Ciba-Geigy Corporation Process for producing triarylphosphites
EP0038876B1 (de) * 1980-04-28 1984-10-10 ADEKA ARGUS CHEMICAL CO., Ltd. 2,6-Di-tertio-butyl-phenyl-pentaerythritol-spiro-bis-phosphite, die die Beständigkeit gegen Wärme und Licht synthetischer Harze erhöhen, Stabilisatorzusammensetzungen, die phenolische Antioxidantien und solche Phosphite enthalten, und synthetische Harzzusammensetzungen, die solche Zusammensetzungen enthalten
US4585818A (en) * 1983-03-31 1986-04-29 Rohm Gmbh Flame retardant polymethyl methacrylate molding compound
US4520149A (en) * 1983-12-01 1985-05-28 Gaf Corporation Elastomer compositions
GB2156358A (en) * 1984-03-23 1985-10-09 Vyzk Ustav Chem Tech Composition for heat and light stabilisation of polymers
US4692539A (en) * 1984-12-24 1987-09-08 Ciba-Geigy Corporation Pentaerythritol diphosphite stabilizers and process
EP0199997A2 (de) * 1985-03-29 1986-11-05 ADEKA ARGUS CHEMICAL CO., Ltd. Verfahren zur Herstellung von Diarylpentaerythritol
US4739090A (en) * 1985-03-29 1988-04-19 Adeka Argus Chemical Co., Ltd. Process for preparing diaryl-pentaerythritol diphosphites
JPS62167338A (ja) * 1986-01-17 1987-07-23 Chisso Corp 難燃性ポリオレフイン組成物

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Patent Abstract of Japan, vol. 3, No. 50 of Japanese Reference No. 54 25951 dated Feb. 27, 1979. *
Patent Abstract of Japan, vol. 3, No. 50 of Japanese Reference No. 54-25951 dated Feb. 27, 1979.
Patent Abstracts of Japan, vol. 5, No. 194, dated Dec. 10, 1981, of Japanese Reference No. 56 113790 dated Sep. 7, 1981. *
Patent Abstracts of Japan, vol. 5, No. 194, dated Dec. 10, 1981, of Japanese Reference No. 56-113790 dated Sep. 7, 1981.

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5308901A (en) * 1988-07-25 1994-05-03 General Electric Company 3-9-diphosphaspiroundecane-stabilized polymer compositions
EP0559461A1 (de) * 1992-03-05 1993-09-08 General Electric Company Vergrösserung der Farbstabilität von Polyolefinzusammensetzungen
US5420184A (en) * 1992-10-14 1995-05-30 Mitsubishi Petrochemical Co., Ltd. Thermoplastic resin composition and process for preparing the same
US5414034A (en) * 1993-03-29 1995-05-09 General Electric Company Processing stabilizer formulations
US6022916A (en) * 1993-03-29 2000-02-08 General Electric Company Processing stabilizer formulations
US5559167A (en) * 1993-07-22 1996-09-24 General Electric Company Gamma irradiated thermoplastics and articles
US5500458A (en) * 1994-09-30 1996-03-19 General Electric Company Phosphite coated polymeric particles
US5786411A (en) * 1996-12-20 1998-07-28 General Electric Company Light resistant compositions of polycarbonate and graft copolymer resins
US6770693B2 (en) 1998-07-13 2004-08-03 Dove Chemical Corporation Blends of phosphites and antioxidants
WO2000023514A1 (en) * 1998-10-21 2000-04-27 Phillips Petroleum Company Phosphite additives in polyolefins
US6613823B1 (en) * 1998-10-21 2003-09-02 Phillips Petroleum Company Phosphite additives in polyolefins
US20030158306A1 (en) * 1998-10-21 2003-08-21 Battiste David R. Phosphite additives in polyolefins
US7135511B2 (en) 1998-10-21 2006-11-14 Chevron Phillips Chemical Company, L.P. Phosphite additives in polyolefins
US20050113494A1 (en) * 2003-11-21 2005-05-26 Bobsein Rex L. Phosphite additives in polyolefins
US7157511B2 (en) 2003-11-21 2007-01-02 Chevron Phillipschemical Company Lp Phosphite additives in polyolefins
CN112585216A (zh) * 2018-08-24 2021-03-30 株式会社可乐丽 聚酰胺组合物和由该聚酰胺组合物形成的成型品
CN112585216B (zh) * 2018-08-24 2024-03-08 株式会社可乐丽 聚酰胺组合物和由该聚酰胺组合物形成的成型品

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DE68916340T2 (de) 1994-12-15
AU623155B2 (en) 1992-05-07
DE68916340D1 (de) 1994-07-28
KR0163028B1 (ko) 1999-01-15
CZ446789A3 (cs) 1998-02-18
CN1023706C (zh) 1994-02-09
PL162422B1 (pl) 1993-12-31
EP0356687A1 (de) 1990-03-07
EP0356687B1 (de) 1994-06-22
JPH0280439A (ja) 1990-03-20
KR910002983A (ko) 1991-02-26
CN1040381A (zh) 1990-03-14
SK278622B6 (en) 1997-11-05
TW198050B (de) 1993-01-11
ES2054944T3 (es) 1994-08-16
CZ283792B6 (cs) 1998-06-17
SK446789A3 (en) 1997-11-05
AU3788289A (en) 1990-01-25

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